EP0321091B1 - Markierung von Oberflächen aus fluorkohlenstoffhaltigen Polymeren - Google Patents

Markierung von Oberflächen aus fluorkohlenstoffhaltigen Polymeren Download PDF

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Publication number
EP0321091B1
EP0321091B1 EP88310668A EP88310668A EP0321091B1 EP 0321091 B1 EP0321091 B1 EP 0321091B1 EP 88310668 A EP88310668 A EP 88310668A EP 88310668 A EP88310668 A EP 88310668A EP 0321091 B1 EP0321091 B1 EP 0321091B1
Authority
EP
European Patent Office
Prior art keywords
fluorocarbon
ptfe
etfe
polymer composition
transmitting
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88310668A
Other languages
English (en)
French (fr)
Other versions
EP0321091A2 (de
EP0321091A3 (en
Inventor
Malcolm George Bradfield
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Balfour Beatty PLC
Original Assignee
BICC PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BICC PLC filed Critical BICC PLC
Priority to AT88310668T priority Critical patent/ATE89842T1/de
Publication of EP0321091A2 publication Critical patent/EP0321091A2/de
Publication of EP0321091A3 publication Critical patent/EP0321091A3/en
Application granted granted Critical
Publication of EP0321091B1 publication Critical patent/EP0321091B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/267—Marking of plastic artifacts, e.g. with laser
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44B—MACHINES, APPARATUS OR TOOLS FOR ARTISTIC WORK, e.g. FOR SCULPTURING, GUILLOCHING, CARVING, BRANDING, INLAYING
    • B44B7/00—Machines, apparatus or hand tools for branding, e.g. using radiant energy such as laser beams
    • B44B7/005—Machines, apparatus or hand tools for branding, e.g. using radiant energy such as laser beams by multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
    • G02B6/4479—Manufacturing methods of optical cables
    • G02B6/4482—Code or colour marking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/34—Apparatus or processes specially adapted for manufacturing conductors or cables for marking conductors or cables
    • H01B13/348—Apparatus or processes specially adapted for manufacturing conductors or cables for marking conductors or cables using radiant energy, e.g. a laser beam
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/146—Laser beam

Definitions

  • This invention relates to a method of marking fluorocarbon surfaces of high-performance electric cables and other articles, and to the products of the method.
  • the insulated conductors (and sometimes composite cores or complete multiconductor cables) need to be marked for the purpose of identifying conductors and circuits, designating cable types, recording the supplier and/or date of manufacture, or for other purposes.
  • Laser printing (which is used for some other cables) is attractive on account of operating without inks or pigment (as e.g.
  • the surface to be coated is either formed of or coated with a reflective flurocarbon polymer composition; a light-transmitting flurocarbon polymer composition comprising an ethylene/tetrafluoroethylene copolymer or an ethylene/chlorotrifluoroethylene copolymer is applied as a surface coating over the surface of the reflective composition; and the coated surface is then marked by laser printing.
  • the reflective fluorocarbon surface is preferably a white pigmented one, more especially one made white by conventional amounts of titanium dioxide pigment. If required however, coloured reflective surfaces can be used, though pastel shades are naturally more satisfactory as background for dark indicia.
  • a “light-transmitting" composition is meant one that is translucent or transparent to the extent that at least 20% of incident radiation of appropriate wavelength (eg about 1000nm if an infra-red laser is to be used) will penetrate the thickness of the surface coating, with or without being scattered , to be reflected by the underlying reflective surface.
  • appropriate wavelength eg about 1000nm if an infra-red laser is to be used
  • ETFE ethylene-tetrafluoro ethylene copolymer
  • PTFE polytetrafluoroethylene
  • FEP fluorinated ethylene/propylene copolymer
  • a suitable mixture of polymers can be used to form the light-transmitting outer layer, but this may produce markings less legible than can be achieved with a layer in which ETFE or ECTFE is the sole polymer. Satisfactory adhesion could also be obtained by etching the pigmented surface (e.g. with a solution of sodium in liquid ammonia), but this is not recommended for products in which the marked surface will be subject to significant electrical stress.
  • a 19 x 0.20mm nickel-plated copper wire strand was coated with a white PTFE composition comprising 0.5% titanium dioxide pigment by a convention extrusion process to form a dielectric of radial thickness 0.25mm.
  • a 16% solids mixed aqueous dispersion comprising only 1 part dispersion grade ETFE and 5 parts dispersion grade PTFE was applied to form a mixed fluorocarbon primer coating about 0.005mm thick.
  • the primed insulated wire was then dried and heated to 375-400°C for half a minute to sinter both the dielectric and the primer.
  • a translucent coating 0.02mm thick was applied by dipping six times in a 35% total solids aqueous dispersion of ETFE with 5% titanium dioxide pigment of mean particle size 0.8nm, each coat being dried and fused at 300°C for half a minute.
  • the resulting coated wire was then laser printed using a 1064nm wavelength YAG laser at nominal beam power of 7W, which formed clearly visible lettering without detriment to electrical properties.
  • coated wire was also receptive of ink jet markings, making it suitable for use also when coloured markings are needed.
  • a 19 x 0.20mm nickel plated copper wire strand was lapped with two "Kapton 616" tapes ("Kapton” is a trademark) each comprising a polyimide film 0.025mm thick coated on each side with 0.0025mm of FEP, applied each with 50% overlap and with opposite hand to form a layer with a radial thickness of 0.12mm.
  • a white coating with a radial thickness of 0.025mm thick was applied to the surface of the tape layer from a 35% total-solids PTFE dispersion containing 12% of the same titanium dioxide pigment.
  • a translucent coating was applied and printed exactly as in Example 1.
  • Example 3 This was exactly the same as Example 3, except that the translucent layer was based on ECTFE instead of ETFE.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Paints Or Removers (AREA)
  • Glass Compositions (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Materials For Medical Uses (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Cereal-Derived Products (AREA)

Claims (14)

  1. Verfahren zum Herstellen einer Fluorkohlenstoff-Oberfläche durch Ausbilden oder Beschichten mit einer reflektierenden Fluorkohlenstoff-Polymerzusammensetzung, gekennzeichnet durch eine lichtdurchlässige fluorkohlenstoffhaltige Polymerzusammensetzung, die ETFE oder ECTFE enthält, als Oberflächenbeschichtung auf der Oberfläche der reflektierenden Zusammensetzung und Markieren der beschichteten Oberfläche durch Bedrucken mittels eines Lasers.
  2. Verfahren nach Anspruch 1, wobei die reflektierende Fluorkohlenstoff-Polymerzusammensetzung Weiß pigmentiert ist.
  3. Verfahren nach Anspruch 1 oder 2, wobei die lichtdurchlässige fluorkohlenstoffhaltige Polymerzusammensetzung lichtdurchlässig ist und 10 bis 50 % der einfallenden Strahlung mindestens einmal innerhalb der lichtdurchlässigen Schicht gestreut wird.
  4. Verfahren nach einem der vorstehenden Ansprüche, wobei die lichtdurchlässige Fluorkohlenstoff-Polymerzusammensetzung aus ETFE gebildet wird.
  5. Verfahren nach Anspruch 4, wobei die reflektierende Fluorkohlenstoff-Polymerzusammensetzung PTFE enthält, wobei vor dem Sintern des PTFE eine Primerbeschichtung aus gemischtem ETFE und PTFE in Dispersion aufgetragen wird.
  6. Verfahren nach Anspruch 4, wobei die reflektierende Fluorkohlenstoff-Polymerzusammensetzung FEP enthält, wobei vor dem Sintern des FEP eine Primerbeschichtung aus gemischtem ETFE und FEP in Dispersion aufgetragen wird.
  7. Verfahren nach einem der vorstehenden Ansprüche zum Markieren der fluorkohlenstoffhaltigen Oberfläche eines isolierten elektrischen Drahts oder Kabels,
  8. Verfahren nach einem der vorstehenden Ansprüche, wobei die lichtdurchlässige Fluorkohlenstoffschicht einen Durchsichtigkeitsgrad hat entsprechend dem bei Einlagerung von 5 bis 6 Gew.-% Titandioxid mit einer mittleren Teilchengröße von 0,8 nm.
  9. Gegenstand mit einer fluorkohlenstoffhaltigen Oberfläche, die durch das Verfahren nach einem der vorstehenden Ansprüche markiert ist.
  10. Gegenstand mit einer Oberfläche aus oder beschichtet mit einer reflektierenden Fluorkohlenstoff-Polymerzusammensetzung, gekennzeichnet durch eine Oberflächenbeschichtung aus einer lichtdurchlässigen fluorkohlenstoffhaltigen Polymerzusammensetzung, die ETFE oder ECTFE enthält, und durch mittels Laser aufgedruckte Markierungen.
  11. Gegenstand nach Anspruch 10, wobei die Oberflächenbeschichtung lichtdurchlässig ist.
  12. Gegenstand nach Anspruch 10, wobei die Oberflächenbeschichtung eine Lichtdurchlässigkeit entsprechend der hat, die man einer 5 bis 6%igen Titandioxidpigmentierung mit einer mittleren Teilchengröße von 0,8 nm erhält.
  13. Gegenstand nach Anspruch 12, wobei die Oberflächenschicht Titandioxid enthält.
  14. Fluorkohlenstoffhaltige Oberfläche zum Bedrucken sowohl mittels Laser als auch mittels Tintenstrahl, mit einer unten liegenden Oberfläche aus weiß pigmentiertem PTFE, einer Primerbeschichtung aus gemischtem PTFE und ETFE und mit einer lichtdurchlässigen Oberflächenschicht aus ETFE.
EP88310668A 1987-11-12 1988-11-11 Markierung von Oberflächen aus fluorkohlenstoffhaltigen Polymeren Expired - Lifetime EP0321091B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88310668T ATE89842T1 (de) 1987-11-12 1988-11-11 Markierung von oberflaechen aus fluorkohlenstoffhaltigen polymeren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB878726482A GB8726482D0 (en) 1987-11-12 1987-11-12 Marking flourocarbon surfaces
GB8726482 1987-11-12

Publications (3)

Publication Number Publication Date
EP0321091A2 EP0321091A2 (de) 1989-06-21
EP0321091A3 EP0321091A3 (en) 1990-11-14
EP0321091B1 true EP0321091B1 (de) 1993-05-26

Family

ID=10626829

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88310668A Expired - Lifetime EP0321091B1 (de) 1987-11-12 1988-11-11 Markierung von Oberflächen aus fluorkohlenstoffhaltigen Polymeren

Country Status (5)

Country Link
US (1) US5091284A (de)
EP (1) EP0321091B1 (de)
AT (1) ATE89842T1 (de)
DE (1) DE3881357D1 (de)
GB (1) GB8726482D0 (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7714217B2 (en) 2007-12-21 2010-05-11 Innovatech, Llc Marked precoated strings and method of manufacturing same
US7811623B2 (en) 2007-12-21 2010-10-12 Innovatech, Llc Marked precoated medical device and method of manufacturing same
US8048471B2 (en) 2007-12-21 2011-11-01 Innovatech, Llc Marked precoated medical device and method of manufacturing same
US8231926B2 (en) 2007-12-21 2012-07-31 Innovatech, Llc Marked precoated medical device and method of manufacturing same
US8231927B2 (en) 2007-12-21 2012-07-31 Innovatech, Llc Marked precoated medical device and method of manufacturing same
US8900652B1 (en) 2011-03-14 2014-12-02 Innovatech, Llc Marked fluoropolymer surfaces and method of manufacturing same

Families Citing this family (34)

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EP0458814A1 (de) * 1989-01-25 1991-12-04 Raychem Corporation Fluorpolymerzusammensetzungen
DE4037875C2 (de) * 1989-11-30 1999-08-26 Sumitomo Electric Industries Mit Fluorharz überzogenes Material mit darauf angebrachten Markierungen
GB9005872D0 (en) * 1990-03-15 1990-05-09 British Aerospace A laser markable white pigment composition
US5247154A (en) * 1991-01-17 1993-09-21 Westinghouse Electric Corp. Method and apparatus for monitoring the laser marking of a bar code label
FR2691670B1 (fr) * 1992-05-26 1994-08-26 Plastic Omnium Cie Ruban en polytétrafluoroéthylène apte au marquage par laser.
US5501827A (en) * 1993-01-29 1996-03-26 Garlock Inc. Laser markable polytetrafluoroethylene resin material and method of making
US5560845A (en) * 1994-02-28 1996-10-01 E. I. Du Pont De Nemours And Company Laser marking of fluoropolymer composition
FR2732030B1 (fr) * 1995-03-20 1997-04-30 Plastic Omnium Cie Meteriau de revetement a base de polytetrafluoroethylene apte au marquage par laser.
US5853955A (en) * 1995-12-11 1998-12-29 Mcdonnell Douglas Corp. Substrates and methods for laser marking same
TW363016B (en) * 1996-01-08 1999-07-01 Nippon Kayaku Kk Laser marking article having two or more layers of thin films on the surface thereof, method for laser marking of the article and ground composition for use in laser marking
DE19630478A1 (de) * 1996-07-27 1998-01-29 Quarzwerke Gmbh Verfahren zur Laserbeschriftung von Folien
EP0922589A1 (de) * 1997-12-10 1999-06-16 Tekmax Inc. Verfahren zur Laserbeschriftung von thermoplastischen Kunststoffen
US6370304B1 (en) 1998-09-28 2002-04-09 Corning Cable Systems Llc Radiation marking of fiber optic cable components
EP1037080A1 (de) * 1999-03-10 2000-09-20 NORDDEUTSCHE SEEKABELWERKE GMBH & CO. KG Kabel, insbesondere Unterwasserkabel
CA2375197A1 (en) * 1999-06-08 2000-12-14 Biomicro Systems, Inc. Laser ablation of doped fluorocarbon materials and applications thereof
US6503310B1 (en) 1999-06-22 2003-01-07 Dmc2 Degussa Metals Catalysts Cerdec Ag Laser marking compositions and method
US6776340B2 (en) * 1999-07-23 2004-08-17 Tri Star Technologies, A General Partnership Duplicate laser marking discrete consumable articles
US6429889B1 (en) 1999-07-23 2002-08-06 Tri-Star Technologies Laser marking discrete consumable articles
US6229114B1 (en) 1999-09-30 2001-05-08 Xerox Corporation Precision laser cutting of adhesive members
US6221552B1 (en) 2000-01-19 2001-04-24 Xerox Corporation Permanent photoreceptor marking system
US6388231B1 (en) 2000-06-15 2002-05-14 Xerox Corporation Systems and methods for controlling depths of a laser cut
US6503316B1 (en) 2000-09-22 2003-01-07 Dmc2 Degussa Metals Catalysts Cerdec Ag Bismuth-containing laser markable compositions and methods of making and using same
US7169471B1 (en) 2003-02-06 2007-01-30 Emd Chemicals, Inc. Laser-marking additive
US6836284B2 (en) * 2003-04-01 2004-12-28 Tri-Star Technologies Laser marking using a digital micro-mirror device
US20050003103A1 (en) * 2003-04-29 2005-01-06 Krupa Robert J. Method for embedding a marking substance in a device such as an insertion tube
US20050214491A1 (en) * 2004-03-23 2005-09-29 3M Innovative Properties Company Cold-shrink marker sleeve
US20050215661A1 (en) * 2004-03-23 2005-09-29 3M Innovative Properties Company NBC-resistant composition
US20060118323A1 (en) * 2004-12-08 2006-06-08 Kalisz Joseph P Wire harness with concentric code identifier
EP2251206A1 (de) 2009-05-15 2010-11-17 Mondi Uncoated Fine & Kraft Paper GmbH Laser- und thermisch beschreibbare Oberflächenbeschichtung für Materialien
CN102555566B (zh) * 2011-12-23 2013-12-25 四川华丰企业集团有限公司 一种在聚四氟乙烯工件上印刷字符的工艺
US10256009B2 (en) 2014-06-19 2019-04-09 Saint-Gobain Performance Plastics Corporation Laser-markable insulation material for wire or cable assemblies
US9881714B2 (en) 2014-06-19 2018-01-30 Saint-Gobain Performance Plastics Corporation Laser-markable insulation material for wire or cable assemblies
DE202014008483U1 (de) * 2014-10-23 2015-10-26 Hellermanntyton Gmbh Kennzeichnungsträger
CN108780201A (zh) 2016-02-19 2018-11-09 通用线缆技术公司 激光可标记的线缆和用于制造其的系统

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US3422215A (en) * 1967-02-16 1969-01-14 Westinghouse Electric Corp Insulated cable
FR2558167A1 (fr) * 1984-01-13 1985-07-19 Du Pont Procede de marquage d'objet en fluoropolymere
US4652528A (en) * 1984-08-13 1987-03-24 Halogen Insulator & Seal Corp. Information carrier and method of use
FR2602904B1 (fr) * 1986-08-05 1989-12-01 Filotex Sa Cable electrique marquable par laser

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7714217B2 (en) 2007-12-21 2010-05-11 Innovatech, Llc Marked precoated strings and method of manufacturing same
US7811623B2 (en) 2007-12-21 2010-10-12 Innovatech, Llc Marked precoated medical device and method of manufacturing same
US7923617B2 (en) 2007-12-21 2011-04-12 Innovatech Llc Marked precoated strings and method of manufacturing same
US8048471B2 (en) 2007-12-21 2011-11-01 Innovatech, Llc Marked precoated medical device and method of manufacturing same
US8231926B2 (en) 2007-12-21 2012-07-31 Innovatech, Llc Marked precoated medical device and method of manufacturing same
US8231927B2 (en) 2007-12-21 2012-07-31 Innovatech, Llc Marked precoated medical device and method of manufacturing same
US8362344B2 (en) 2007-12-21 2013-01-29 Innovatech, Llc Marked precoated strings and method of manufacturing same
US8574171B2 (en) 2007-12-21 2013-11-05 Innovatech, Llc Marked precoated medical device and method of manufacturing same
US8772614B2 (en) 2007-12-21 2014-07-08 Innovatech, Llc Marked precoated strings and method of manufacturing same
US8940357B2 (en) 2007-12-21 2015-01-27 Innovatech Llc Marked precoated medical device and method of manufacturing same
US9355621B2 (en) 2007-12-21 2016-05-31 Innovatech, Llc Marked precoated strings and method of manufacturing same
US8900652B1 (en) 2011-03-14 2014-12-02 Innovatech, Llc Marked fluoropolymer surfaces and method of manufacturing same

Also Published As

Publication number Publication date
EP0321091A2 (de) 1989-06-21
ATE89842T1 (de) 1993-06-15
GB8726482D0 (en) 1987-12-16
US5091284A (en) 1992-02-25
DE3881357D1 (de) 1993-07-01
EP0321091A3 (en) 1990-11-14

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